Methods for selective deposition of metal silicides via atomic layer deposition cycles

ABSTRACT

Methods for selectively depositing a metal silicide layer are provided herein. In some embodiments, a method of selectively depositing a metal silicide layer includes: (a) providing a substrate having a first layer to a process chamber, wherein the first layer comprises a first surface and a feature formed in the first surface comprising an opening defined by one or more sidewalls and a bottom surface wherein the sidewalls comprise one of silicon oxide or silicon nitride and wherein the bottom surface comprises at least one of silicon or germanium; (b) exposing the substrate to a precursor gas comprising a metal halide; (c) purging the precursor gas from the process chamber using an inert gas; (d) exposing the substrate to a silicon containing gas; (e) purging the silicon containing gas from the process chamber using an inert gas; (f) repeating (b)-(e) to selectively deposit a metal silicide along the bottom surface to a predetermined thickness; and (g) annealing the substrate after depositing the metal silicide layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of U.S. provisional patent applicationSer. No. 62/155,963, filed May 1, 2015, which is herein incorporated byreference in its entirety.

FIELD

Embodiments of the present disclosure generally relate to methods ofselectively depositing a metal silicide layer via atomic layerdeposition cycles.

BACKGROUND

The formation of a logic-contact structure typically involves formationof a metal silicide at the bottom of a feature. The inventors haveobserved that when forming a contact within a narrow feature (e.g., 10nm or less), metal may deposit along the sidewalls of the feature aswell as at the bottom of the feature. The metal formation along thesidewalls reduces the amount of conductive fill material that can bedeposited within the feature, resulting in an undesirable increase inthe contact resistance.

Accordingly, the inventors have developed improved techniques toselectively deposit a metal silicide layer via atomic layer depositioncycles.

SUMMARY

Methods for selectively depositing a metal silicide layer are providedherein. In some embodiments, a method of selectively depositing a metalsilicide layer includes: (a) providing a substrate having a first layerto a process chamber, wherein the first layer comprises a first surfaceand a feature formed in the first surface comprising an opening definedby one or more sidewalls and a bottom surface, wherein the sidewallscomprise one of silicon oxide or silicon nitride and wherein the bottomsurface comprises at least one of silicon or germanium; (b) exposing thesubstrate to a precursor gas comprising a metal halide; (c) purging theprecursor gas from the process chamber using an inert gas; (d) exposingthe substrate to a silicon containing gas; (e) purging the siliconcontaining gas from the process chamber using an inert gas; (f)repeating (b)-(e) to selectively deposit a metal silicide along thebottom surface to a predetermined thickness; and (g) annealing thesubstrate after depositing the metal silicide layer.

In some embodiments, a method of selectively depositing a metal silicidelayer, includes: (a) providing a substrate having a first layer to aprocess chamber, wherein the first layer comprises a first surface and afeature formed in the first surface comprising an opening having a widthof less than about 10 nm and defined by one or more sidewalls and abottom surface, wherein the sidewalls comprise one of silicon oxide orsilicon nitride and wherein the bottom surface comprises at least one ofsilicon or germanium; (b) exposing the substrate to a precursor gascomprising a metal halide; (c) purging the precursor gas from theprocess chamber using an inert gas; (d) exposing the substrate to asilicon containing gas; (e) purging the silicon containing gas from theprocess chamber using an inert gas; f) repeating (b)-(e) to selectivelydeposit a metal silicide along the bottom surface to a predeterminedthickness; (g) annealing the substrate for about 1 millisecond to about1 minute after depositing the metal silicide layer; (h) depositing acapping layer within the feature after depositing and annealing themetal silicide layer; (i) depositing a liner layer atop the cappinglayer; and (j) depositing a conductive fill material atop the linerlayer to substantially fill the feature.

In some embodiments, a computer readable medium, having instructionsstored thereon which, when executed, cause a process chamber to performa method for selectively depositing a metal silicide layer are providedherein. The method may include any of the embodiments disclosed herein.

Other and further embodiments of the present disclosure are describedbelow.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments of the present disclosure, briefly summarized above anddiscussed in greater detail below, can be understood by reference to theillustrative embodiments of the disclosure depicted in the appendeddrawings. However, the appended drawings illustrate only typicalembodiments of the disclosure and are therefore not to be consideredlimiting of scope, for the disclosure may admit to other equallyeffective embodiments.

FIG. 1 depicts a flow chart of a method for selectively depositing ametal silicide layer in accordance with some embodiments of the presentdisclosure.

FIGS. 2A-2C depict the stages of selectively depositing a metal silicidelayer in accordance with some embodiments of the present disclosure.

FIG. 3 depicts a process chamber suitable for performing a method ofselectively depositing a metal silicide layer in accordance with someembodiments of the present disclosure.

To facilitate understanding, identical reference numerals have beenused, where possible, to designate identical elements that are common tothe figures. The figures are not drawn to scale and may be simplifiedfor clarity. Elements and features of one embodiment may be beneficiallyincorporated in other embodiments without further recitation.

DETAILED DESCRIPTION

Methods for selectively depositing a metal silicide layer are providedherein. The inventive methods advantageously facilitate selectivelydepositing a metal silicide layer at the bottom of a feature (forexample, a contact) and not along the sidewalls (or to a much lesserdegree). By selectively depositing a metal silicide layer along thebottom of the feature, the metal silicide layer takes up less space inthe feature. The smaller amount of metal silicide in the featureadvantageously results in improved resistance because there is a greateramount of conductive fill material in the feature. The inventive methodsmay be utilized in the formation of metal interconnects in an integratedcircuit, or in the formation of a metal gate or a metal-contact gap fillprocess, as well as other suitable applications utilizing filling afeature with a conductive material.

FIG. 1 depicts a flow chart of a method 100 for selectively depositing ametal silicide layer in accordance with some embodiments of the presentdisclosure. The method 100 is described below with respect to the stagesof selectively depositing a metal silicide layer as depicted in FIGS.2A-2C and may be performed, for example, in a suitable reactor, such asis described below with respect to FIG. 3.

The method 100 starts at 102 by providing a substrate, such as thesubstrate 200, to a processing volume of a substrate processing chamber,for example process chamber 302 described below with respect to FIG. 3.In some embodiments, as shown in FIG. 2A, the substrate 200 includes afirst layer 212 having a first surface 213 with one or more features202, formed in the first surface 213 of the substrate 200, and extendingtowards a base 204 of the substrate 200. In some embodiments, thefeature 202 may be etched partially into the base 204 of the substrate200. The substrate 200 may be any suitable substrate having the one ormore features 202 formed in the substrate 200. For example, thesubstrate 200 may comprise one or more of silicon (Si), germanium,silicon germanium, doped or undoped polysilicon, doped or undopedsilicon wafers and patterned or non-patterned wafers silicon oninsulator (SOI), doped silicon, or the like. The substrate 200 may havevarious dimensions, such as 200 mm, 300 mm or 450 mm diameter wafers orother dimensions. In some embodiments, the substrate 200 comprises atleast one of silicon or germanium. In some embodiments, the first layer212 comprises silicon oxide (SiOx) or silicon nitride (SiN). Inaddition, the substrate 200 may include additional layers of materialsor may have one or more completed or partially completed structures ordevices formed in or on the substrate 200.

The feature 202 may be formed by etching the substrate 200 using anysuitable etch process. In some embodiments, the feature 202 comprises anopening 218 defined by one or more sidewalls 214 and a bottom surface206. In some embodiments, the feature 202 may be a via, contact, trench,dual damascene, or the like. In some embodiments, the opening 218 mayhave a width of less than about 10 nm. The feature 202 is formed in thesubstrate 200 or in layers disposed atop the substrate such that thebottom surface 206 is a different material than the predominant surfacesof the one or more sidewalls 214. For example, the feature 202 may be anopening 218 formed in the first layer 212 and extending deep enough suchthat the bottom surface 206 is formed by the substrate 200. In someembodiments, the substrate 200 (and as such the bottom surface 206)comprises silicon, germanium, or silicon germanium, and the first layer212 (and as such the one or more sidewalls 214) comprises silicon oxideor silicon nitride.

Next at 104, as depicted in FIG. 2B, the substrate 200 is exposed to aprecursor gas comprising a metal halide, such as a metal chloride, aspart of the process to selectively deposit the metal silicide layer 220at the bottom surface 206 of the feature 202 but not on the sidewalls214 of the feature 202, or with very little deposition on the sidewalls214. Selective deposition on the bottom surface 206 means that materialis deposited on the bottom surface 206 at a greater rate than on the oneor more sidewalls 214, or in some embodiments, at a much greater rate(e.g., at least one order of magnitude greater) than on the one or moresidewalls 214. In some embodiments, no material is deposited on thesidewalls 214. However, while a predominant amount of material isdeposited on the bottom surface 206, some deposition may occur on theone or more sidewalls 214. By selectively depositing the metal silicidelayer predominantly or solely along the bottom of the feature, the metalsilicide layer takes up less space in the feature than if there were asimilar amount of metal silicide deposited along the one or moresidewalls. The smaller amount of metal silicide in the featurefacilitates depositing a greater amount of conductive fill material inthe feature, advantageously providing improved resistance.

The metal silicide layer comprises tantalum, hafnium, zirconium, ortungsten. In some embodiments, the metal halide is any suitable metalhalide to deposit a metal silicide layer comprising one of tantalum,hafnium, zirconium, or tungsten. In some embodiments, the metal halideis a metal chloride, such as tantalum pentachloride (TaCl₅), hafniumtetrachloride (HfCl₄), zirconium tetrachloride (ZrCl₄), tungstenhexachloride (WCl₆), or tungsten pentachloride (WCl₅). In someembodiments, the precursor gas further comprises an inert gas, such asargon, helium, or the like. In some embodiments, the precursor gas maybe provided at a flow rate of up to about 500 sccm. In some embodiments,a temperature of the process chamber of about 350 degrees Celsius toabout 550 degrees Celsius. In some embodiments, a pressure of theprocess chamber during exposure to the precursor gas may be maintainedat about 2 Torr to about 15 Torr. In some embodiments, the substrate maybe exposed to the precursor gas for about 1 to about 10 seconds.

In some embodiments, prior to exposing the substrate 200 to theprecursor gas, the substrate is exposed to a cleaning process to remove,for example, a native oxide layer on the bottom surface 206 of thefeature 202. In some embodiments, the substrate is exposed to a remoteNH₃/NF₃ plasma to provide highly selective SiO₂/Si removal by formingNH₄F which is easy to react with Si—O or Si—N bonds at room temperature,but not with Si—Si bonds. The polymer NH₄F—SiO₂ can be sublimated andetched away when sufficiently heated.

Next, at 106, the processing volume of the process chamber is purged ofthe precursor gas. In some embodiments, the precursor gas is purgedusing any suitable inert gas, for example argon, xenon, helium, or thelike.

Next, at 108, the substrate 200 is exposed to a silicon containing gascomprising silane (SiH₄) or derivatives thereof (e.g., disilane,trisilane, tetrasilane, chlorosilane, dichlorosilane, tetrachlorosilane,hexachlorodisilane, methylsilane, or the like). In some embodiments, thesilicon containing gas may be provided at a flow rate of up to about 500sccm. In some embodiments, the temperature of the process chamber may bemaintained at about 350 degrees Celsius to about 550 degrees Celsius. Insome embodiments, a pressure of the process chamber during exposure tothe silicon containing gas may be about 2 Torr to about 15 Torr. In someembodiments, the substrate may be exposed to the silicon containing gasfor about 0.5 to about 5 seconds. The inventors have observed that thesilane or derivatives thereof described above react with chlorine wherethe precursor gas is a metal chloride.

Next, at 110, the processing volume of the process chamber is purged ofthe silicon containing gas. In some embodiments, the silicon containinggas is purged using any suitable inert gas, for example argon, xenon,helium, or the like. Alternately exposing the substrate to the metalhalide and the silicon containing gas selectively deposits a thin layerof metal silicide along the bottom surface of the substrate. Theinventors have observed that the metal halide precursor and the silanereact with the termination of the chemical bonds, for example thesilicon bonds, at the bottom surface of the feature to form the metalsilicide predominantly along the bottom surface but not along theoxidized or nitridized sidewalls of the feature. As indicated at 112,104-110 may be repeated to selectively deposit the metal silicide alongthe bottom surface of the substrate to a predetermined thickness whileadvantageously not depositing, or depositing very little, metal silicidealong the one or more sidewalls of the of the feature.

Next, at 114, the substrate 200 may be annealed after depositing themetal silicide layer 220. In some embodiments, the anneal temperature isabout 500 degrees Celsius to about 1100 degrees Celsius. In someembodiments, the substrate 200 is annealed for about 1 millisecond toabout 1 minute. In some embodiments, the anneal helps to form a stablemetal silicide structure, for example a stable tantalum silicide (TaSi₂)structure.

In some embodiments, as depicted in FIG. 2C, after formation of themetal silicide layer, a capping layer 222 may be deposited within thefeature 202. The capping layer may advantageously limit or preventoxidation of the metal silicide layer. A “capping layer,” as usedherein, may refer to a layer conformably formed along at least a portionof the sidewalls and/or lower surface of a feature such that asubstantial portion of the feature prior to the deposition of the layerremains unfilled after deposition of the layer. In some embodiments, thecapping layer 222 may be formed along the entirety of the sidewalls andlower surface of the feature. In some embodiments, the capping layer 222is a metal containing layer. For example, in some embodiments, thecapping layer 222 may contain tungsten (W), aluminum (Al), titanium(Ti), tantalum (Ta), oxides or nitrides thereof, silicides thereof,derivatives thereof, or combinations thereof. In some embodiments, thecapping layer 222 is titanium nitride. The capping layer 222 may beformed by any process suitable to provide the capping layer 222 having asuitable thickness. For example, in some embodiments, the capping layer222 may be formed via a deposition process, such as chemical vapordeposition (CVD), physical vapor deposition (PVD), or a cyclicaldeposition process, for example, such as atomic layer deposition (ALD),or the like.

In some embodiments, a liner layer 224 may be deposited within thefeature 202. A “liner layer,” as used herein, refers to a layerconformably formed along at least a portion of the sidewalls and/orlower surface of an opening such that a substantial portion of theopening prior to the deposition of the layer remains unfilled afterdeposition of the layer. In some embodiments, the liner layer 224 may beformed along the entirety of the sidewalls and bottom surface of theopening. In some embodiments, the liner layer 224 may comprise anymaterial suitable to act as a liner. For example, in some embodiments,the liner layer 224 may comprise a metal, for example, one or more oftitanium (Ti), tantalum (Ta), cobalt (Co), manganese (Mn), tungsten (W),hafnium (Hf), alloys thereof, or the like. The liner layer 224 may beformed by any process suitable to provide the liner layer 224 having asuitable thickness. For example, in some embodiments, the liner layer224 may be formed via a deposition process, such as chemical vapordeposition (CVD), physical vapor deposition (PVD), or a cyclicaldeposition process, for example, such as atomic layer deposition (ALD),or the like.

Following formation of the capping layer 222 and the liner layer 224,the feature 202 may be filled with a conductive fill material 226. Forexample, in some embodiments, the conductive fill material 226 may beone or more of copper, cobalt, tungsten, or the like. The conductivefill material 226 may be deposited in the feature 202 using any suitabledeposition process, such as CVD or PVD.

FIG. 3 depicts a schematic diagram of an illustrative apparatus 300 ofthe kind that may be used to practice embodiments of the disclosure asdiscussed herein. The apparatus 300 may be any apparatus suitable forperforming one or more substrate processes, for example but not limitedto, deposition process such as chemical vapor deposition (CVD), atomiclayer deposition (ALD), or the like. In some embodiments the processchamber 302 may be a standalone apparatus 300, as depicted below, or athe process chamber 302 may be part of a cluster tool, such as any ofthe CENTURA®, PRODUCER®, or ENDURA® cluster tools available from AppliedMaterials, Inc. of Santa Clara, Calif.

The apparatus 300 may comprise a controller 350 and a process chamber302 having an exhaust system 320 for removing excess process gases,processing by-products, or the like, from the inner volume 305 of theprocess chamber 302. Exemplary process chambers may include any ofseveral process chambers configured for chemical vapor deposition (CVD)or atomic layer deposition (ALD), available from Applied Materials, Inc.of Santa Clara, Calif. Other suitable process chambers from othermanufacturers may similarly be used.

The process chamber 302 has an inner volume 305 that may include aprocessing volume 304. The processing volume 304 may be defined, forexample, between a substrate support 308 disposed within the processchamber 302 for supporting a substrate 310 during processing and one ormore gas inlets, such as a showerhead 314 and/or nozzles provided atsuitable locations. In some embodiments, the substrate support 308 mayinclude a mechanism that retains or supports the substrate 310 on thesurface of the substrate support 308, such as an electrostatic chuck, avacuum chuck, a substrate retaining clamp, or the like (not shown). Insome embodiments, the substrate support 308 may include mechanisms forcontrolling the substrate temperature (such as heating and/or coolingdevices, not shown) and/or for controlling the species flux and/or ionenergy proximate the substrate surface.

For example, in some embodiments, the substrate support 308 may includean RF bias electrode 340. The RF bias electrode 340 may be coupled toone or more bias power sources (one bias power source 338 shown) throughone or more respective matching networks (matching network 336 shown).The one or more bias power sources may be capable of producing up to1200 W or RF energy at a frequency of about 2 MHz to about 60 MHz, suchas at about 2 MHz, or about 13.56 MHz, or about 60 Mhz. In someembodiments, two bias power sources may be provided for coupling RFpower through respective matching networks to the RF bias electrode 340at respective frequencies of about 2 MHz and about 13.56 MHz. The atleast one bias power source may provide either continuous or pulsedpower. In some embodiments, the bias power source alternatively may be aDC or pulsed DC source.

The substrate 310 may enter the process chamber 302 via an opening 312in a wall of the process chamber 302. The opening 312 may be selectivelysealed via a slit valve 318, or other mechanism for selectivelyproviding access to the interior of the chamber through the opening 312.The substrate support 308 may be coupled to a lift mechanism 334 thatmay control the position of the substrate support 308 between a lowerposition (as shown) suitable for transferring substrates into and out ofthe chamber via the opening 312 and a selectable upper position suitablefor processing. The process position may be selected to maximize processuniformity for a particular process. When in at least one of theelevated processing positions, the substrate support 308 may be disposedabove the opening 312 to provide a symmetrical processing region.

The one or more gas inlets (e.g., the showerhead 314) may be coupled toa gas supply 316 for providing one or more process gases through a massflow controller 317 into the processing volume 304 of the processchamber 302. In addition, one or more valves 319 may be provided tocontrol the flow of the one or more process gases. The mass flowcontroller 317 and one or more valves 319 may be used individually, orin conjunction, to provide the process gases at predetermined flowrates, such as at a constant flow rate, or pulsed.

Although a showerhead 314 is shown in FIG. 3, additional or alternativegas inlets may be provided such as nozzles or inlets disposed in theceiling or on the sidewalls of the process chamber 302 or at otherlocations suitable for providing gases to the process chamber 302, suchas the base of the process chamber, the periphery of the substratesupport, or the like.

The apparatus 300 has the capability to utilize capacitively coupled RFenergy for plasma processing. For example, the process chamber 302 mayhave a ceiling 342 made from dielectric materials and a showerhead 314that is at least partially conductive to provide an RF electrode (or aseparate RF electrode may be provided). The showerhead 314 (or other RFelectrode) may be coupled to one or more RF power sources (one RF powersource 348 shown) through one or more respective matching networks(matching network 346 shown). The one or more plasma sources may becapable of producing up to about 3,000 W, or in some embodiments, up toabout 5,000 W, of RF energy at a frequency of about 2 MHz and/or about13.56 MHz or a high frequency, such as 27 MHz and/or 60 MHz. The exhaustsystem 320 generally includes a pumping plenum 324 and one or moreconduits that couple the pumping plenum 324 to the inner volume 305 (andgenerally, the processing volume 304) of the process chamber 302.

A vacuum pump 328 may be coupled to the pumping plenum 324 via a pumpingport 326 for pumping out the exhaust gases from the process chamber viaone or more exhaust ports (two exhaust ports 322 shown). The vacuum pump328 may be fluidly coupled to an exhaust outlet 332 for routing theexhaust to appropriate exhaust handling equipment. A valve 330 (such asa gate valve, or the like) may be disposed in the pumping plenum 324 tofacilitate control of the flow rate of the exhaust gases in combinationwith the operation of the vacuum pump 328. Although a z-motion gatevalve is shown, any suitable, process compatible valve for controllingthe flow of the exhaust may be utilized.

To facilitate control of the process chamber 302 as described above, thecontroller 350 may be any form of general-purpose computer processorthat can be used in an industrial setting for controlling variouschambers and sub-processors. The memory, or computer-readable medium,356 of the CPU 352 may be one or more of readily available memory suchas random access memory (RAM), read only memory (ROM), floppy disk, harddisk, or any other form of digital storage, local or remote. The supportcircuits 354 are coupled to the CPU 352 for supporting the processor ina conventional manner. These circuits include cache, power supplies,clock circuits, input/output circuitry and subsystems, and the like.

The inventive methods disclosed herein may generally be stored in thememory 356 as a software routine 358 that, when executed by the CPU 352,causes the process chamber 302 to perform processes of the presentdisclosure. The software routine 358 may also be stored and/or executedby a second CPU (not shown) that is remotely located from the hardwarebeing controlled by the CPU 352. Some or all of the method of thepresent disclosure may also be performed in hardware. As such, thedisclosure may be implemented in software and executed using a computersystem, in hardware as, e.g., an application specific integrated circuitor other type of hardware implementation, or as a combination ofsoftware and hardware. The software routine 358 may be executed afterthe substrate 310 is positioned on the substrate support 308. Thesoftware routine 358, when executed by the CPU 352, transforms thegeneral purpose computer into a specific purpose computer (controller)350 that controls the chamber operation such that the methods disclosedherein are performed.

The disclosure may be practiced using other semiconductor substrateprocessing systems wherein the processing parameters may be adjusted toachieve acceptable characteristics by those skilled in the art byutilizing the teachings disclosed herein without departing from thespirit of the disclosure.

While the foregoing is directed to embodiments of the presentdisclosure, other and further embodiments of the disclosure may bedevised without departing from the basic scope thereof.

The invention claimed is:
 1. A method of selectively depositing a metalsilicide layer, comprising: (a) providing a substrate having a firstlayer to a process chamber, wherein the first layer comprises a firstsurface and a feature formed in the first surface comprising an openingdefined by one or more sidewalls and a bottom surface, wherein thesidewalls comprise one of silicon oxide or silicon nitride and whereinthe bottom surface comprises at least one of silicon or germanium; (b)exposing the substrate to a cleaning process comprising exposing thesubstrate to a remote plasma of a mixture of a fluorine-containingprecursor and a hydrogen-containing precursor; (c) exposing thesubstrate to a precursor gas comprising a metal halide; (d) purging theprecursor gas from the process chamber using an inert gas; (e) exposingthe substrate to a silicon containing gas comprising silane orderivatives thereof; (f) purging the silicon containing gas from theprocess chamber using an inert gas; (g) repeating (c)-(f) to selectivelydeposit a predominant amount of a metal silicide along the bottomsurface to a predetermined thickness, wherein at least some depositionof the metal silicide occurs on the one or more sidewalls, and whereinthe metal silicide comprises one of tantalum, hafnium, zirconium, ortungsten; and (h) annealing the substrate after depositing the metalsilicide layer.
 2. The method of claim 1, wherein the opening has awidth of less than about 10 nm.
 3. The method of claim 1, wherein theprecursor gas further comprises an inert gas.
 4. The method of claim 1,wherein a flow rate of the precursor gas and the silicon containing gasare each up to about 500 sccm.
 5. The method of claim 1, wherein atemperature of the process chamber during exposure to the precursor gasand exposure to the silicon containing gas is about 350 degrees Celsiusto about 550 degrees Celsius.
 6. The method of claim 1, wherein apressure of the process chamber during exposure to the precursor gas andexposure to the silicon containing gas is about 2 Tarr to about 15 Tarr.7. The method of claim 1, wherein the substrate is exposed to theprecursor gas for about 1 to about 10 seconds.
 8. The method of claim 1,wherein the precursor gas is one of tantalum pentachloride (TaCl₅),hafnium tetrachloride (HfCl₄), zirconium tetrachloride (ZrCl₄), tungstenhexachloride (WCl₆), or tungsten pentachloride (WCl₅).
 9. The method ofclaim 1, wherein the substrate is exposed to the silicon containing gasfor about 0.5 to about 5 seconds.
 10. The method of claim 1, wherein atemperature of the substrate during the anneal is about 500 degreesCelsius to about 1100 degrees Celsius.
 11. The method of claim 1,wherein the substrate is annealed for about 1 millisecond to about 1minute.
 12. The method of claim 1, further comprising depositing acapping layer within the feature after deposition of the metal silicidelayer.
 13. The method of claim 12, wherein the capping layer comprisestitanium nitride (TiN).
 14. The method of claim 12, further comprisingdepositing a liner layer atop the capping layer.
 15. The method of claim14, wherein the liner layer comprise one or more of titanium (Ti),tantalum (Ta), cobalt (Co), manganese (Mn), tungsten (W), or hafnium(Hf).
 16. The method of claim 15, further comprising depositing aconductive fill material to substantially fill the feature.
 17. A methodof selectively depositing a metal silicide layer, comprising: (a)providing a substrate having a first layer to a process chamber, whereinthe first layer comprises a first surface and a feature formed in thefirst surface comprising an opening having a width of less than about 10nm and defined by one or more sidewalls and a bottom surface, whereinthe sidewalls comprise one of silicon oxide or silicon nitride andwherein the bottom surface comprises at least one of silicon orgermanium; (b) exposing the substrate to a cleaning process comprisingexposing the substrate to a remote plasma of a mixture of afluorine-containing precursor and a hydrogen-containing precursor; (c)exposing the substrate to a precursor gas comprising a metal halide forabout 1 to about 10 seconds, wherein a flow rate of the precursor gas isup to about 500 sccm and wherein a pressure of the process chamberduring exposure to the precursor gas is about 2 Tarr to about 15 Tarr;(d) purging the precursor gas from the process chamber using an inertgas; (e) exposing the substrate to a silicon containing gas comprisingsilane or derivatives thereof for about 0.5 to about 5 seconds, whereina flow rate of the silicon containing gas is up to about 500 sccm andwherein a pressure of the process chamber during exposure to the siliconcontaining gas is about 2 Torr to about 15 Torr; (f) purging the siliconcontaining gas from the process chamber using an inert gas; (g)repeating (c)-(f) to selectively deposit a predominant amount of a metalsilicide along the bottom surface to a predetermined thickness, whereinat least some deposition of the metal silicide occurs on the one or moresidewalls, and wherein the metal silicide comprises one of tantalum,hafnium, zirconium, or tungsten; (h) annealing the substrate at atemperature of about 500 to about 1100 degrees Celsius for about 1millisecond to about 1 minute after depositing the metal silicide layer;(i) depositing a capping layer within the feature after depositing andannealing the metal silicide layer; (j) depositing a liner layer atopthe capping layer; and (k) depositing a conductive fill material atopthe liner layer to substantially fill the feature.
 18. The method ofclaim 17, wherein the precursor gas is one of tantalum pentachloride(TaCl₅), hafnium tetrachloride (HfCl₄), zirconium tetrachloride (ZrCl₄),tungsten hexachloride (WCl₆), or tungsten pentachloride (WCl₅).
 19. Anon-transitory computer readable medium, having instructions storedthereon which, when executed, cause a process chamber to perform amethod for selectively depositing a metal silicide layer on a substratehaving a first layer, wherein the first layer comprises a first surfaceand a feature formed in the first surface comprising an opening definedby one or more sidewalls and a bottom surface wherein the sidewallscomprise one of silicon oxide or silicon nitride and wherein the bottomsurface comprises at least one of silicon or germanium, the methodcomprising: (a) exposing the substrate to a cleaning process comprisingexposing the substrate to a remote plasma of a mixture of afluorine-containing precursor and a hydrogen-containing precursor; (b)exposing the substrate to a precursor gas comprising a metal halide; (c)purging the precursor gas from the process chamber using an inert gas;(d) exposing the substrate to a silicon containing gas comprising silaneor derivatives thereof; (e) purging the silicon containing gas from theprocess chamber using an inert gas; (f) repeating (b)-(e) to selectivelydeposit a predominant amount of a metal silicide along the bottomsurface to a predetermined thickness, wherein at least some depositionof the metal silicide occurs on the one or more sidewalls, and whereinthe metal silicide comprises one of tantalum, hafnium, zirconium, ortungsten; and (g) annealing the substrate after depositing the metalsilicide layer.